Para-phenylene diamine polymer color improvement with sequestering agent

ABSTRACT

A process is provided for increasing the brightness and decreasing the discoloration of PPD polymer during the polymer production. Sequestering agents having a stability constant (K 1 ), for Fe(III), greater than about 12 are slurried with the PPD polymer in water and then rinsed, neutralized, and dried.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Para-phenylene diamine (PPD) polymer is subject to an excessive and,until now, uncontrolled and unpredictable discoloration in isolation ofthe polymer from low-temperature solution polymerization. Discoloredpolymer yields discolored products and, even if the discoloration isnot, of itself, unacceptable, discoloration of inconsistent degrees maywell be unacceptable. This invention relates to a process for preparingPPD polymer having an improved color uniformity from run to run.

2. Description of the Prior Art

Prior to the present invention, it has been the practice to isolate PPDpolymer from the solution polymerization media by washing in waterwithout particular regard to the wash water or materials containedtherein.

U.S. Pat. No. 4,308,374, issued Dec. 29, 1981 on the application ofVollbracht et al. discloses that poly-p-phenylene terephthalamide isisolated by mixing the reaction mixture with water or aqueous alkali.There is no mention of treatment to control discoloration in the polymerproduct.

U.S. Pat. Nos. 3,819,587 and 3,869,429, issued June 25, 1974 and Mar. 4,1975 on the applications of Kwolek and Blades, respectively, disclosethat polyamides are isolated by being vigorously stirred with water andthen filtered. Those patents, further, state that one of the washes maycontain sodium carbonate or hydroxide. Neither patent is concerned withpolymer discoloration.

Japanese Application Publication (Kokai) 58-40,306, published Mar. 9,1983 discloses addition of alkali metal or ammonium salt ofethyenediaminetetraacetic acid to water-soluble acrylic copolymers tomaintain the polymer water-solubility during pulverization. There is nomention of polymer discoloration.

U.S. Pat. No. 4,650,624, issued Mar. 17, 1987 on the application ofReinehr et al., discloses that EDTA can be used to increase thewhiteness of dry spun acrylic fibers. The EDTA is added to the spinningsolution and has nothing to do with production of the acrylic polymer.

U.S. Pat. No. 3,415,611, issued Dec. 10, 1968 on the application ofCallahan et al., discloses that EDTA can be used to increase thewhiteness of wet spun acrylonitrile fibers. The EDTA is added to thespinning solution or to spun fibers in the gel state and has nothing todo with production of the acrylonitrile polymer.

SUMMARY OF THE INVENTION

The present invention provides a process for preparing PPD polymer ofreduced discoloration wherein polymer isolation from the solutionpolymerization medium includes treatment with a sequestering agent. Thesequestering agent can be any aminocarboxylic acid having a stabilityconstant (K₁), for Fe(III), of greater than about 12; and the treatmentshould include addition of the sequestering agent to the unisolated PPDpolymer before the pH of the polymer system has been raised above 2. ThePPD polymer which is most usually used in practice of this invention ispoly(p-phenylene terephthalamide) (PPD-T).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation of Color L (Brightness) versus theconcentration of sequestering agent used for treating PPD-T by theprocess of this invention.

FIG. 2 is a graphical representation of Color L (Brightness) versus thepH of the treatment system at constant concentration of sequesteringagent to show that practice of the process of this invention issubstantially independent of pH below a pH of about 8 or 9.

DETAILED DESCRIPTION OF THE INVENTION

Discoloration of PPD polymer during the polymer production, has been acontinuing problem. At some times, there have been excessivediscoloration and from time-to-time in the same process there have beenvarying degrees of discoloration. It has been desired to minimize thediscoloration and to make the degree of color uniform over a long courseof polymer production.

Although the reason for the effect is not entirely understood, it hasnow been discovered that discoloration of PPD polymer can be decreasedand controlled by addition of particular sequestering agents to thepolymer system prior to final washing and drying. The sequesteringagents can be added to PPD polymer newly-isolated from thepolymerization system before neutralization, that is, before the PPDpolymer has been exposed to a pH greater than about 2, and, preferablybefore a pH greater than about 1. The sequestering agent could be addedto the polymerization system before the polymerization is completed ifit doesn't interfere with the polymerization reaction.

By PPD polymer is meant any polymer resulting from mole-for-molepolymerization of p-phenylene diamine with a coreactant and, also,copolymers resulting from incorporation of other diamines with thep-phenylene diamine. As a general rule, other diamines can be used inamounts up to as much as about 50 mole percent of the total diamine. Itis believed that discoloration of PPD polymers is caused by impuritiesin the PPD or generated by reaction of the PPD; and that thediscoloration can be decreased by the process of the present inventionin polymers having at least 25 total mole percent PPD.

The present invention has been most often used with PPD-T. By PPD-T ismeant the homopolymer resulting from mole-for-mole polymerization ofp-phenylene diamine and terephthaloyl chloride and, also, copolymersresulting from incorporation of small amounts of other diamines with thep-phenylene diamine and of small amounts of other diacid chlorides withthe terephthaloyl chloride. As a general rule, other diamines and otherdiacid chlorides can be used in amounts up to as much as about 10 molepercent of the p-phenylene diamine or the terephthaloyl chloride, orperhaps slightly higher, provided only that the other diamines anddiacid chlorides have no reactive groups which interfere with thepolymerization reaction. PPD-T, also, means copolymers resulting fromincorporation of other aromatic diamines and other aromatic diacidchlorides such as, for example, 2,6-naphthaloyl chloride or choroordichloroterephthaloyl chloride; provided, only, that the other aromaticdiamines and aromatic diacid chlorides be present in amounts whichpermit preparation of anisotropic spin dopes. Preparation of PPD-T isdescribed in U.S. Pat. Nos. 3,869,429; 4,308,374; and 4,698,414.

PPD polymer, for treatment by the process of this invention, is preparedby polymerization in a liquid medium and is isolated from thepolymerization system by washing with water. The treatment process ofthis invention can be conducted in the polymerization system or in anyof the washes. The process is preferably conducted in the first wash, atfirst contact of the polymer with water and before the pH of the systemis greater than 2 and, preferably, before the pH is greater that 1. Thepolymerization system for PPD-T generally yields a product which is agranular, solid, mass with a dry appearance; but containing only about5-15% PPD-T. That polymer product is named herein, and is well-known byworkers in this art to be, "acid crumb".

In conduct of the process of this invention, the acid crumb is combinedwith water in an amount adequate to yield an aqueous slurry of thepolymer. Water is usually used in an amount 5 to 50 times the weight ofthe polymer in the crumb and with the sequestering agent in anappropriate amount. The combination of PPD polymer, sequestering agent,and water is agitated for a time adequate to permit contact ofsubstantially all of the PPD polymer with the sequestering agent. A timeof as little as 10 seconds of agitation has been deemed to be adequatefor systems having efficient agitation. The process of this inventioncan be conducted in a batch manner or as a continuous process; carebeing taken, in the case of a continuous process, to maintain theamounts of the various component streams within the appropriate ranges.

Sequestering agents useful in the practice of this invention includecompounds having stability constants, for Fe(III), of greater than about12. Sequestering agents which are particularly useful areaminocarboxylic acids having K₁ >12 for Fe(III). Particularly preferredare ethylenediamine tetraacetic acid (EDTA) having K₁ =25.1 andnitrilotriacetic acid (NTA) having K₁ =15.9 for Fe(III). It has beenconcluded that sequestering agents having low stability constants arenot effective in this invention. For example, it has been found thatcitric acid having K₁ =11.4 for Fe(III) and sodium tripolyphosphatehaving K₁ =3.6 for Fe(III) cannot be used to practice this invention.

The benefits of this invention are realized by addition of any amount ofsequestering agent. Very small amounts of the agent may yield smallimprovement. Generally, good results are obtained by use of about 0.25to 0.75% of the sequestering agent based on the weight of PPD polymer tobe treated. As stated, less of the agent can be used for diminishedeffect. Noticeable improvement in brightness can be obtained by aslittle as 0.1% EDTA based on weight of PPD polymer. More than 0.75% ofthe sequestering agent can be used; but amounts in excess of about 0.75%do not appear to provide substantial additional benefit. The brightnessof PPD polymer treated by 3.0% sequestering agent is about the same asPPD polymer treated by 0.75% of the same agent.

Color determinations are made using a Hunter Lab Tristimulus Colorimetermodel D25M-9 such as that sold by Hunterlab of Reston, Va., U.S.A.Brightness of polymer for this invention was determined by measuring the"L" color component. The "L" color component is a measure of theblackness or whiteness of a polymer sample on a scale from 0 (black) to100 (white).

For the purposes of this invention, the absolute values of the "L" valuedetermined from the test are not important. The differences in colorbetween treated and untreated polymers are easily seen by relativevalues from the treated polymers to the controls. Color improvementsresulting from practice of this invention can be determined using anysensitive colorimeter to compare treated and untreated polymers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE 1

This example describes practice of the process of this invention usingEDTA and PPD-T.

PPD-T was made in accordance with the teachings of U.S. Pat. No.4,308,374 to yield an acid crumb of about 11% polymer and having a dryappearance. Three hundred weight parts of the acid crumb were mixed with500 weight parts of distilled water to form a slurry. The pH of theslurry was about 0.6. It was estimated that the filter cake containedabout 33 weight parts of PPD-T. To the slurry of PPD-T, still beingmixed, was added 0.25 weight parts of EDTA sequestering agent (0.75%,based on the weight of the PPD-T). The pH of the system was adjusted to6.0 using sodium hydroxide solution, and the system was agitated forabout ten more minutes.

After mixing the polymer with the sequestering agent, the system wasfiltered and the filter cake was slurried and filtered four more timesusing about 750 weight parts of water each time. Finally, the filtercake was dried in an oven for about 16 hours at about 140° C.

As a control, the above procedure was followed omitting addition of thesequestering agent.

Color determinations were conducted on the products of this example inaccordance with the color determination test method described above. Itshould be noted that color differences of only two units on the colorscale are easily detected by the unaided eye. The color of the polymertreated by this invention was 78.0 and the color of the control was68.2.

EXAMPLE 2

In this example, the procedure of Example 1 was followed with theexception that different amounts of sequestering agent were added to theslurry in different runs. Results of the several runs are shown in thethe table, below, and are, also, depicted in the graphicalrepresentation of FIG. 1. The column headed "ΔL" shows the colordifference between the treated PPD-T and the Control PPD-T. Note thatthe runs of this example were conducted on polymer made on threedifferent occasions and that, as a consequence, the color of thecontrols is slightly different from batch to batch.

    ______________________________________                                        Batch    % sequestering agent                                                                           Color L  ΔL                                   ______________________________________                                        I        None (control)   73.2     --                                                  0.03             75.1     1.9                                                 0.75             78.6     5.4                                                 3.00             78.5     5.3                                        II       None (control)   68.2     --                                                  0.15             76.5     8.3                                                 0.30             75.8     7.6                                                 0.45             76.9     8.7                                                 0.75             76.8     8.6                                                 3.00             77.1     8.9                                        III      None (control)   68.0     --                                                  0.03             69.1     1.1                                                 0.06             71.9     3.9                                                 0.09             72.1     4.1                                                 0.12             76.7     8.7                                                 0.15             70.8     2.8                                                 0.75             78.1     10.1                                                0.75             80.3     12.3                                       ______________________________________                                    

EXAMPLE 3

In this example, the procedure of Example 1 was followed with theexception that the pH of the initial slurry was adjusted to havedifferent values for different runs. Results of the several runs areshown in the table, below, and are, also, depicted in the graphicalrepresentation of FIG. 2. The amount of sequestering agent wasmaintained at 0.75%, based on polymer weight. The control was PPD-Tmaintained at pH 6 with no sequestering agent treatment.

    ______________________________________                                        pH             Color L                                                        ______________________________________                                         6 (control)   69.0                                                            1             82.2                                                            3             81.6                                                            4             79.4                                                            5             80.8                                                            6             80.9                                                            7             81.6                                                            8             80.7                                                            9             78.6                                                           10             78.0                                                           11             76.7                                                           ______________________________________                                    

EXAMPLE 4

In this example, the procedure of Example 1 was followed with theexception that different sequestering agents were used for differentruns. Results of the runs are shown in the table, below. The amount ofsequestering agent was maintained at 0.75%, based polymer weight.

    ______________________________________                                        Sequestering Agent  Color L  L                                                ______________________________________                                        None (control)      69.0     --                                               Na.sub.2 EDTA*      78.6     9.6                                              Na.sub.2 NTA**      78.6     9.6                                              Na.sub.3 Citric Acid***                                                                           71.9     2.9                                              Sodium Tripolyphosphate                                                                           71.4     2.4                                              ______________________________________                                         *disodium salt of EDTA                                                        **disodium salt of NTA                                                        ***trisodium salt of Citric Acid                                         

What is claimed is:
 1. A process for treating para-phenylene diamine(PPD) polymer comprising the steps of:(a) combining PPD polymer,newly-isolated from a PPD polymer polymerization system, at least 0.1%,based on weight of the PPD polymer, of a sequestering agent having astability constant (K₁), for Fe(III), of greater than 12, and water inan amount adequate to yield a slurry of the PPD polymer; (b) agitatingthe combination for at least ten seconds; (c) separating the PPD polymerfrom the combination.
 2. The process of claim 1 wherein the PPD polymeris poly(p-phenylene terephthalamide) (PPD-T).
 3. The process of claim 1comprising additional steps of:(d) combining the separated PPD polymerwith water in an amount adequate to yield a slurry of the PPD polymer;(e) agitating the combination for at least ten seconds; (f) separatingthe PPD polymer from the combination; (g) optionally, repeating steps(d), (e), and (f).
 4. The process of claim 1 wherein the newly-isolatedPPD polymer is combined before it has been exposed to a pH greater thanabout
 2. 5. A process for treating poly(p-phenylene terephthalamide)(PPD-T) comprising the steps of:(a) combining PPD-T acid crumb, at least0.1%, based on weight of the PPD-T, of a sequestering agent having astability constant (K₁), for Fe(III), of greater than 12, and water inan amount adequate to yield a slurry of the PPD-T; (b) agitating thecombination for at least ten seconds; (c) separating the PPD-T from thecombination.
 6. The process of claim 5 wherein the acid crumb iscombined before it has been exposed to a pH greater that about
 2. 7. Theprocess of claim 5 wherein the sequestering agent is an aminocarboxylicacid.
 8. The process of claim 7 wherein the aminocarboxylic acid isethylenediamine tetraacetic acid.
 9. The process of claim 7 wherein theaminocarboxylic acid is nitrilotriacetic acid.
 10. The process of claim5 wherein the water is in an amount of 5 to 50 times the weight of thePPD-T.